U.S. patent application number 14/895875 was filed with the patent office on 2016-04-21 for dinuclear metallocene compound, and a method for preparing the same.
The applicant listed for this patent is LG CHEM, LTD.. Invention is credited to Yoon Hee CHO, Young Shil DO, Seung Hwan JUNG, Choong Hoon LEE, Ji Joong MOON, Sang Eun PARK.
Application Number | 20160108069 14/895875 |
Document ID | / |
Family ID | 52474779 |
Filed Date | 2016-04-21 |
United States Patent
Application |
20160108069 |
Kind Code |
A1 |
DO; Young Shil ; et
al. |
April 21, 2016 |
DINUCLEAR METALLOCENE COMPOUND, AND A METHOD FOR PREPARING THE
SAME
Abstract
The present invention relates to a dinuclear metallocene
compound with a new structure which can manufacture polyolefin
having high molecular weight and to a method for preparing the
same. The dinuclear metallocene compound according to the present
invention is a dinuclear metallocene compound with a new structure,
and, unlike a single-site catalyst, has high accessibility to a
substrate, and thus, can provide a multi-site catalyst with high
activity.
Inventors: |
DO; Young Shil; (Daejeon,
KR) ; LEE; Choong Hoon; (Daejeon, KR) ; JUNG;
Seung Hwan; (Daejeon, KR) ; MOON; Ji Joong;
(Daejeon, KR) ; CHO; Yoon Hee; (Daejeon, KR)
; PARK; Sang Eun; (Daejeon, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
LG CHEM, LTD. |
Yeongdeungpo-gu, Seoul |
|
KR |
|
|
Family ID: |
52474779 |
Appl. No.: |
14/895875 |
Filed: |
December 27, 2013 |
PCT Filed: |
December 27, 2013 |
PCT NO: |
PCT/KR2013/012320 |
371 Date: |
December 3, 2015 |
Current U.S.
Class: |
546/4 |
Current CPC
Class: |
C07F 17/00 20130101;
C07F 7/28 20130101; C08F 4/76 20130101 |
International
Class: |
C07F 7/28 20060101
C07F007/28; C08F 4/76 20060101 C08F004/76 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 25, 2013 |
KR |
10-2013-0073043 |
Dec 27, 2013 |
KR |
10-2013-0165067 |
Claims
1. A dinuclear metallocene compound represented by the following
Chemical Formula 1: ##STR00009## in the Chemical Formula 1, R1 to
R4 may be identical to or different from each other, and are
independently hydrogen; a halogen radical; an alkyl radical having
a carbon number of 1 to 20; an alkenyl radical having a carbon
number of 2 to 20; a silyl radical; an aryl radical having a carbon
number of 6 to 20; an alkylaryl radical having a carbon number of 7
to 20; or an arylalkyl radical having a carbon number of 7 to 20;
and two or more adjacent radicals of R1 to R4 may be linked each
other to form an aliphatic ring, or an aromatic ring; R5 to R7 may
be identical to or different from each other, and are independently
hydrogen; a halogen radical; an alkyl radical having a carbon
number of 1 to 20; an alkenyl radical having a carbon number of 2
to 20; an aryl radical having a carbon number of 6 to 20; an
alkylaryl radical having a carbon number of 7 to 20; an arylalkyl
radical having a carbon number of 7 to 20; an alkoxy radical having
a carbon number of 1 to 20; an aryloxy radical having a carbon
number of 6 to 20; or an amido radical; and two or more adjacent
radicals of R5 to R7 may be linked each other to form an aliphatic
ring, or an aromatic ring; CY is an aliphatic or aromatic ring
containing nitrogen, and may be unsubstituted or substituted with
halogen, an alkyl or aryl radical having a carbon number of 1 to
20, and if it has multiple substituents, two or more substituents
may be linked each other to form an aliphatic or aromatic ring; M
is Group 4 transition metal; X1 is a halogen radical; an alkyl
radical having a carbon number of 1 to 20; an alkenyl radical
having a carbon number of 2 to 20; an aryl radical having a carbon
number of 6 to 20; an alkylaryl radical having a carbon number of 7
to 20; an arylalkyl radical having a carbon number of 7 to 20; an
alkylamido radical having a carbon number of 1 to 20; an arylamido
radical having a carbon number of 6 to 20; or an alkylidene radical
having a carbon number of 1 to 20; and n is an integer of 0 to
10.
2. The dinuclear metallocene compound according to claim 1, wherein
R1 to R7 are independently hydrogen, an alkyl group having a carbon
number of 1 to 20, or an aryl group having a carbon number of 6 to
20, and CY is a pentagonal or hexagonal aliphatic or aromatic ring
containing nitrogen, unsubstituted or substituted with an alkyl
group having a carbon number of 1 to 20, M is titanium (Ti),
zirconium (Zr), or hafnium (Hf), and X1 is halogen or an alkyl
group having a carbon number of 1 to 20.
3. The dinuclear metallocene compound according to claim 1, wherein
the compound of the Chemical Formula 1 is represented by the
following structures: ##STR00010##
4. A method for preparing a dinuclear metallocene compound
represented by the following Chemical Formula 1, comprising the
step of reacting a compound represented by the following Chemical
Formula 2 with a compound represented by the following Chemical
Formula 3: ##STR00011## in the Chemical Formulae 1, 2 and 3, R1 to
R4 may be identical to or different from each other, and are
independently hydrogen; a halogen radical; an alkyl radical having
a carbon number of 1 to 20; an alkenyl radical having a carbon
number of 2 to 20; a silyl radical; an aryl radical having a carbon
number of 6 to 20; an alkylaryl radical having a carbon number of 7
to 20; or an arylalkyl radical having a carbon number of 7 to 20;
and two or more adjacent radicals of R1 to R4 may be linked each
other to form an aliphatic ring, or an aromatic ring; R5 to R7 may
be identical to or different from each other, and are independently
hydrogen; a halogen radical; an alkyl radical having a carbon
number of 1 to 20; an alkenyl radical having a carbon number of 2
to 20; an aryl radical having a carbon number of 6 to 20; an
alkylaryl radical having a carbon number of 7 to 20; an arylalkyl
radical having a carbon number of 7 to 20; an alkoxy radical having
a carbon number of 1 to 20; an aryloxy radical having a carbon
number of 6 to 20; or an amido radical; and two or more adjacent
radicals of R5 to R7 may be linked each other to form an aliphatic
ring, or an aromatic ring; CY is an aliphatic or aromatic ring
containing nitrogen, and may be unsubstituted or substituted with
halogen, an alkyl or aryl radical having a carbon number of 1 to
20, and if it has multiple substituents, two or more substituents
may be linked each other to form an aliphatic or aromatic cring; M
is Group 4 transition metal; X1 and X2 may be identical to or
different from each other, and are independently a halogen radical;
an alkyl radical having a carbon number of 1 to 20; an alkenyl
radical having a carbon number of 2 to 20; an aryl radical having a
carbon number of 6 to 20; an alkylaryl radical having a carbon
number of 7 to 20; an arylalkyl radical having a carbon number of 7
to 20; an alkylamido radical having a carbon number of 1 to 20; an
arylamido radical having a carbon number of 6 to 20; or an
alkylidene radical having a carbon number of 1 to 20; and n is an
integer of 0 to 10.
5. The method for preparing a dinuclear metallocene compound
according to claim 4, wherein the step of reacting the compound
represented by the Chemical Formula 2 with the compound represented
by the Chemical Formula 3 is conducted by stirring at a temperature
of -30 to 25.degree. C.
6. The method for preparing a dinuclear metallocene compound
according to claim 4, wherein the step of reacting the compound
represented by the Chemical Formula 2 with the compound represented
by the Chemical Formula 3 is conducted in MTBE (methyl
tertiary-butyl ether), or toluene solvent.
Description
BACKGROUND OF THE INVENTION
[0001] (a) Field of the Invention
[0002] The present invention relates to a dinuclear metallocene
compound, and a method for preparing the same. More specifically,
the present invention relates to a dinuclear metallocene compound
with a novel structure which can prepare polyolefin having high
molecular weight, and a method for preparing the same.
[0003] This application claims the benefits of filing dates of
Korean Patent Application No. 10-2013-0073043 filed with Korean
Intellectual Property Office on Jun. 25, 2013, and Korean Patent
Application No. 10-2013-0165067 filed with Korean Intellectual
Property Office on Dec. 27, 2013, the entire contents of which are
incorporated herein by reference.
[0004] (b) Description of the Related Art
[0005] Since a Zeigler-Natta catalyst widely applied in an
industrial process is a multi-site catalyst, the molecular weight
distribution of the produced polymer is wide, and the composition
distribution of comonomers is not uniform, and thus, has a
limitation in securing desired properties.
[0006] Meanwhile, a metallocene catalyst is a single-site catalyst
having one kind of an active site, and it has advantages in that
the molecular weight distribution of the produced polymer is
narrow, and that the molecular weight, stereoregularity,
crystallinity, particularly reactivity of comonomers may be greatly
controlled according to the structure of the catalyst and the
ligand. However, polyolefin polymerized using a metallocene
catalyst has narrow molecular weight distribution, and if applied
for some products, productivity is remarkably decreased due to
extrusion load and the like, rendering site application difficult,
and thus, there have been many attempts to control the molecular
weight distribution of polyolefin
[0007] For this, a method of using a mononuclear metallocene
compound and a dinuclear metallocene compound is known.
[0008] As an example of the mononuclear metallocene compound, U.S.
Pat. No. 5,032,562 describes a method of preparing a polymerization
catalyst by supporting two different transition metal catalysts on
one carrier. This is a method of producing bimodal distribution
polymer by supporting a titanium (Ti)-based Ziegler Natta catalyst
producing high molecular weight and a zirconium (Zr)-based
metallocene catalyst producing low molecular weight on one carrier,
however, it has disadvantages in that the supporting process is
complicated, and the morphology of polymer becomes worse due to a
cocatalyst.
[0009] And, studies on changing copolymer selectivity and activity
of a catalyst in copolymerization using a dinuclear metallocene
compound has been reported, and in case of some metallocene
catalysts, copolymer incorporation and activity increase have been
reported.
[0010] For example, Korean Patent Application No. 2003-12308
discloses a method of controlling molecular weight distribution by
supporting a dinuclear metallocene catalyst and a mononuclear
metallocene catalyst on a carrier together with an activator and
polymerizing while changing the combination of catalysts in the
reactor. However, this method has a limitation in simultaneously
realizing the properties of each catalyst, and has a disadvantage
in that a metallocene catalyst part is dissociated in the carrier
component of the final catalyst, thus causing fouling of a
reactor.
[0011] And, a synthesis method of a Group 4 metallocene catalyst
having a biphenylene bridge and polymerization of ethylene and
styrene using the same have been reported (Organometallics, 2005,
24, 3618). According to this method, it is stated that catalytic
activity is high and the molecular weight of the obtained polymer
is high, compared to a mononuclear metallocene catalyst. It has
been also reported that reactivity of a catalyst may be changed by
converting the bridge structure of Group 4 dinuclear metallocene
catalyst (Eur. Polym, J. 2007, 43, 1436).
[0012] However, if using these methods, previously reported Group 4
metallocene catalyst having a biphenylene bridge has problems in
terms of addition of substituents and modification of a structure.
Therefore, there is a need for development of novel metallocene
catalyst useful for preparation of olefin.
SUMMARY OF THE INVENTION
[0013] In order to solve the above problem, it is an object of the
invention to provide a novel dinuclear metallocene compound, which
can prepare polyolefin having high molecular weight with high
activity.
[0014] It is another object of the invention to provide a method
for preparing the dinuclear metallocene compound.
[0015] In order to achieve the objects, one aspect of the invention
provides a dinuclear metallocene compounds represented by the
following Chemical Formula 1:
##STR00001##
[0016] in the Chemical Formula 1,
[0017] R1 to R4 may be identical to or different from each other,
and are independently hydrogen; a halogen radical; an alkyl radical
having a carbon number of 1 to 20; an alkenyl radical having a
carbon number of 2 to 20; a silyl radical; an aryl radical having a
carbon number of 6 to 20; an alkylaryl radical having a carbon
number of 7 to 20; or an arylalkyl radical having a carbon number
of 7 to 20; and two or more adjacent radicals of R1 to R4 may be
linked each other to form an aliphatic ring, or an aromatic
ring;
[0018] R5 to R7 may be identical to or different from each other,
and are independently hydrogen; a halogen radical; an alkyl radical
having a carbon number of 1 to 20; an alkenyl radical having a
carbon number of 2 to 20; an aryl radical having a carbon number of
6 to 20; an alkylaryl radical having a carbon number of 7 to 20; an
arylalkyl radical having a carbon number of 7 to 20; an alkoxy
radical having a carbon number of 1 to 20; an aryloxy radical
having a carbon number of 6 to 20; or an amido radical; and two or
more adjacent radicals of R5 to R7 may be linked each other to form
an aliphatic ring, or an aromatic ring;
[0019] CY is an aliphatic or aromatic ring containing nitrogen, and
may be unsubstituted or substituted with halogen, an alkyl or aryl
radical having a carbon number of 1 to 20, and if it has multiple
substituents, two or more substituents may be linked each other to
form an aliphatic or aromatic ring;
[0020] M is Group 4 transition metal;
[0021] X1 is a halogen radical; an alkyl radical having a carbon
number of 1 to 20; an alkenyl radical having a carbon number of 2
to 20; an aryl radical having a carbon number of 6 to 20; an
alkylaryl radical having a carbon number of 7 to 20; an arylalkyl
radical having a carbon number of 7 to 20; an alkylamido radical
having a carbon number of 1 to 20; an arylamido radical having a
carbon number of 6 to 20; or an alkylidene radical having a carbon
number of 1 to 20; and
[0022] n is an integer of 0 to 10.
[0023] Another aspect of the invention provides a method for
preparing the dinuclear metallocene compound.
[0024] The dinuclear metallocene compound according to the present
invention is a novel dinuclear metallocene compound, and the
dinuclear metallocene compound has high accessibility to a
substrate unlike a single-site catalyst Thus, the present invention
can provide a multi-site catalyst with high activity.
[0025] And, using the catalyst of the present invention, polyolefin
having high molecular weight can be produced.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0026] As used herein, terms "a first", "a second" and the like are
used to explain various constructional elements, and they are used
only to distinguish one constructional element from other
constructional elements.
[0027] And, the terms used herein are only to explain illustrative
examples, and are not intended to limit the invention. A singular
expression includes a plural expression thereof, unless it is
expressly stated or obvious from the context that such is not
intended. As used herein, the terms "comprise", "contain" or "have"
and the like are intended to designate the existence of practiced
characteristic, number, step, constructional element or
combinations thereof, and they are not intended to preclude the
possibility of existence or addition of one or more other
characteristics, numbers, steps, constructional elements or
combinations thereof.
[0028] And, in case it is stated that each constructional element
is formed "on" or "above" each construction element, it means that
each constructional element is formed directly on each
constructional element, or that other constructional elements may
be additionally formed between the layers or on the object or
substrate.
[0029] Although various modifications can be made to the present
invention and the present invention may have various forms,
specific examples will be illustrated and explained in detail
below. However, it should be understood that these are not intended
to limit the present invention to specific disclosure, and that the
present invention includes all the modifications, equivalents or
replacements thereof without departing from the spirit and
technical scope of the invention.
[0030] Hereinafter, the present invention will be explained in
detail.
[0031] According to one aspect of the invention, provided is a
dinuclear metallocene compounds represented by the following
Chemical Formula 1:
##STR00002##
[0032] in the Chemical Formula 1,
[0033] R1 to R4 may be identical to or different from each other,
and are independently hydrogen; a halogen radical; an alkyl radical
having a carbon number of 1 to 20; an alkenyl radical having a
carbon number of 2 to 20; a silyl radical; an aryl radical having a
carbon number of 6 to 20; an alkylaryl radical having a carbon
number of 7 to 20; or an arylalkyl radical having a carbon number
of 7 to 20; and two or more adjacent radicals of R1 to R4 may be
linked each other to form an aliphatic ring, or an aromatic
ring;
[0034] R5 to R7 may be identical to or different from each other,
and are independently hydrogen; a halogen radical; an alkyl radical
having a carbon number of 1 to 20; an alkenyl radical having a
carbon number of 2 to 20; an aryl radical having a carbon number of
6 to 20; an alkylaryl radical having a carbon number of 7 to 20; an
arylalkyl radical having a carbon number of 7 to 20; an alkoxy
radical having a carbon number of 1 to 20; an aryloxy radical
having a carbon number of 6 to 20; or an amido radical; and two or
more adjacent radicals of R5 to R7 may be linked each other to form
an aliphatic ring, or an aromatic ring;
[0035] CY is an aliphatic or aromatic ring containing nitrogen, and
may be unsubstituted or substituted with halogen, an alkyl or aryl
radical having a carbon number of 1 to 20, and if it has multiple
substituents, two or more substituents may be linked each other to
form an aliphatic or aromatic ring;
[0036] M is Group 4 transition metal;
[0037] X1 is a halogen radical; an alkyl radical having a carbon
number of 1 to 20; an alkenyl radical having a carbon number of 2
to 20; an aryl radical having a carbon number of 6 to 20; an
alkylaryl radical having a carbon number of 7 to 20; an arylalkyl
radical having a carbon number of 7 to 20; an alkylamido radical
having a carbon number of 1 to 20; an arylamido radical having a
carbon number of 6 to 20; or an alkylidene radical having a carbon
number of 1 to 20; and
[0038] n is an integer of 0 to 10.
[0039] According to one embodiment of the invention, in the
dinuclear metallocene compound of the Chemical Formula 1, R1 to R7
are independently hydrogen, an alkyl group having a carbon number
of 1 to 20, or an aryl group having a carbon number of 6 to 20, or
two or more adjacent radicals of R1 to R7 may be linked each other
to form one or more aliphatic ring, or aromatic ring, but the
present invention is not limited thereto.
[0040] And, CY may be a pentagonal or hexagonal aliphatic or
aromatic ring containing nitrogen, unsubstituted or substituted
with an alkyl group having a carbon number of 1 to 20, but the
present invention is not limited thereto.
[0041] And, M may be titanium (Ti), zirconium (Zr), or hafnium
(Hf), and X1 may be halogen or an alkyl group having a carbon
number of 1 to 20, but the present invention is not limited
thereto.
[0042] The dinuclear metallocene compound represented by the
Chemical Formula 1 includes a structure wherein two single
metallocene compounds respectively bridged with a phenylene group
having a cyclic amido group introduced therein are crosslinked by
alkylenedioxy (--O--(CH.sub.2)--(CH.sub.2)n-(CH.sub.2)--O--). Thus,
two metal centers are connected by a diether chain functioning as a
linker, to reduce unnecessary interactions between the metals, thus
affording stable catalytic activity and easiness of structural
deformation, and unlike a single-site catalyst, the compound has
high accessibility to a substrate and thus exhibits high activity.
Thus, by using the dinuclear metallocene compound as a catalyst for
polymerization or copolymerization of polyolefin, polyolefin having
high molecular weight and wide molecular weight distribution can be
produced with high activity. And, various substituents may be
introduced into the cyclopentadienyl and the cyclic amido ring such
as quinoline or indoline, which ultimately enables easy controlling
of electronic, steric environment around the metals. Namely, by
using the compound with such a structure, the structure and
properties and the like of prepared olefin polymer may be easily
controlled.
[0043] Examples of the dinuclear metallocene compound represented
by the Chemical Formula 1 include the following compounds, but are
not limited thereto.
##STR00003##
[0044] According to another aspect of the invention, provided is a
method for preparing a dinuclear metallocene compound represented
by the following Chemical Formula 1, comprising a step of reacting
a compound represented by the following Chemical Formula 2 with a
compound represented by the following Chemical Formula 3:
##STR00004##
[0045] in the Chemical Formulae 1, 2 and 3,
[0046] R1 to R4 may be identical to or different from each other,
and are independently hydrogen; a halogen radical; an alkyl radical
having a carbon number of 1 to 20; an alkenyl radical having a
carbon number of 2 to 20; a silyl radical; an aryl radical having a
carbon number of 6 to 20; an alkylaryl radical having a carbon
number of 7 to 20; or an arylalkyl radical having a carbon number
of 7 to 20; and two or more adjacent radicals of R1 to R4 may be
linked each other to form an aliphatic ring, or an aromatic
ring;
[0047] R5 to R7 may be identical to or different from each other,
and are independently hydrogen; a halogen radical; an alkyl radical
having a carbon number of 1 to 20; an alkenyl radical having a
carbon number of 2 to 20; an aryl radical having a carbon number of
6 to 20; an alkylaryl radical having a carbon number of 7 to 20; an
arylalkyl radical having a carbon number of 7 to 20; an alkoxy
radical having a carbon number of 1 to 20; an aryloxy radical
having a carbon number of 6 to 20; or an amido radical; and two or
more adjacent radicals of R5 to R7 may be linked each other to form
an aliphatic ring, or an aromatic ring;
[0048] CY is an aliphatic or aromatic ring containing nitrogen, and
may be unsubstituted or substituted with halogen, an alkyl or aryl
radical having a carbon number of 1 to 20, and if it has multiple
substituents, two or more substituents may be linked each other to
form an aliphatic or aromatic ring;
[0049] M is Group 4 transition metal;
[0050] X1 and X2 may be identical to or different from each other,
and are independently a halogen radical; an alkyl radical having a
carbon number of 1 to 20; an alkenyl radical having a carbon number
of 2 to 20; an aryl radical having a carbon number of 6 to 20; an
alkylaryl radical having a carbon number of 7 to 20; an arylalkyl
radical having a carbon number of 7 to 20; an alkylamido radical
having a carbon number of 1 to 20; an arylamido radical having a
carbon number of 6 to 20; or an alkylidene radical having a carbon
number of 1 to 20; and
[0051] n is an integer of 0 to 10.
[0052] The method for preparing a dinuclear metallocene compound
may be conducted by mixing the mononuclear metallocene compound
represented by the Chemical Formula 2 with the diol compound
represented by the Chemical Formula 3, and then, stirring for a
certain time. The stirring temperature may be about -30 to about
25.degree. C., preferably room temperature, and the stirring time
may be 12 hours or more, for example, about 12 hours to about 36
hours, but not limited thereto. And, the stirring may be conducted
in an organic solvent such as MTBE (methyl tertiary-butyl ether) or
toluene, and a dinuclear metallocene compound may be obtained by
extracting in n-hexane, but the preparation method of the invention
is not limited thereto.
[0053] The diol compound represented by the Chemical Formula 3 may
react at 0.5 equivalents to the mononuclear metallocene compound
represented by the Chemical Formula 2.
[0054] The dinuclear metallocene compound represented by the
Chemical Formula 1 may be prepared according to any methods known
in the technical field to which the invention pertains, without
specific limitations.
[0055] The method for preparing a dinuclear metallocene compound
represented by the Chemical Formula 1 will be illustrated and
explained in detail in the examples below.
[0056] According to the preparation method of the present
invention, a dinuclear metallocene compound represented by the
Chemical Formula 1 may be prepared by a simple process under
relatively mild conditions, and by controlling the distance between
dinuclear active sites according to the length of the alkyl chain
of a diol compound, activity may be easily controlled while
reducing unnecessary interactions. And, the compound has stable
catalytic activity and the structural deformation is easy, and
unlike a single-site catalyst, it has high accessibility to a
substrate and thus exhibits high activity.
[0057] The dinuclear metallocene compound represented by the
Chemical Formula 1 may be used as a catalyst composition alone or
in combination with a cocatalyst to prepare polyolefin polymer, and
particularly, it may produce polyolefin having high molecular
weight with high activity. For example, a catalyst composition
comprising the dinuclear metallocene compound represented by the
Chemical Formula 1 may be contacted with monomers to conduct a
polymerization process, thereby providing olefin homopolymer or
olefin copolymer.
[0058] Hereinafter, the actions and the effects of the invention
will be explained in detail, with reference to specific examples.
However, these examples are only presented to illustrate the
invention, and the right scope of the invention is not determined
thereby.
EXAMPLE
[0059] The organic reagents and solvents used in the following
examples, unless specifically mentioned, were purchased from
Aldrich Company, purified by a standard method and used. In all the
synthesis steps, contact of air with moisture was blocked to
increase reproducibility of the experiments.
Synthesis of Dinuclear Metallocene Compound
Example 1
##STR00005##
[0061]
([(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-eta5-
, kappa-N]titanium dimethyl) (1 g, 3.04 mmol) was dissolved in a
methyl tertiary-butyl ether (40 mL) solvent. And then, it was
slowly added dropwise to a solution of 1,6-hexanediol (180 mg, 1.52
mmol) dissolved in methyl tertiary-butyl ether (20 mL) at
-20.degree. C. The temperature of an orange solution was slowly
raised and the solution was stirred at room temperature (25.degree.
C.) for 36 hours.
[0062] After removing the methyl tertiary-butyl ether solvent, 30
ml of n-hexane was added to filter, and then, a desired compound in
the form of orange solid was obtained (1.0 g, 95% or more
yield).
[0063] .sup.1H NMR (CDCl.sub.3): .delta. 1.26 (s, 3H,
Ti--CH.sub.3), 1.85 (m, 6H, Cp-CH.sub.3), 1.00.about.2.00 (br, 6H,
diol aliphatic (CH.sub.2).sub.2, quinoline-CH.sub.2), 2.13 (m, 6H,
Cp-CH.sub.3 and CH.sub.3), 2.61 (m, 2H, quinoline-CH.sub.2), 3.77
(br, 2H, OCH.sub.2), 4.16 (m, 2H, quinoline-NCH.sub.2), 6.64 (m,
1H, aromatic), 6.91 (m, 2H, aromatic) ppm
Example 2
##STR00006##
[0065]
([(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-eta5-
, kappa-N]titanium dimethyl) (1 g, 3.04 mmol) was dissolved in a
methyl tertiary-butyl ether (40 mL) solvent. And then, it was
slowly added dropwise to a solution of 1,4-butanediol (140 mg, 1.55
mmol) dissolved in methyl tertiary-butyl ether (20 mL) at
-20.degree. C. The temperature of an orange solution was slowly
raised and the solution was stirred at room temperature (25.degree.
C.) for 36 hours.
[0066] After removing the methyl tertiary-butyl ether solvent, 30
mL of n-hexane was added to filter, and a desired compound in the
form of orange solid was obtained (1.0 g, 95% or more yield).
[0067] .sup.1H NMR (CDCl.sub.3): .delta. 1.26 (s, 3H,
Ti--CH.sub.3), 1.85 (m, 6H, Cp-CH.sub.3), 1.00.about.2.00 (br, 4H,
diol aliphatic (CH.sub.2), quinoline-CH.sub.2), 2.13 (m, 6H,
Cp-CH.sub.3 and CH.sub.3), 2.62 (m, 2H, quinoline-CH.sub.2), 3.79
(br, 2H, OCH.sub.2), 4.17 (m, 2H, quinoline-NCH.sub.2), 6.64 (m,
1H, aromatic), 6.89 (m, 2H, aromatic) ppm
Example 3
##STR00007##
[0069]
([(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-eta5-
, kappa-N]titanium dimethyl) (1 g, 3.04 mmol) was dissolved in a
methyl tertiary-butyl ether (40 mL) solvent. And then, it was
slowly added dropwise to a solution of 1,3-propanediol (115 mg,
1.51 mmol) dissolved in methyl tertiary-butyl ether (20 mL) at
-20.degree. C. The temperature of an orange solution was slowly
raised and the solution was stirred at room temperature (25.degree.
C.) for 36 hours.
[0070] After removing the methyl tertiary-butyl ether solvent, 30
mL of n-hexane was added to filter, and a desired compound in the
form of orange solid was obtained (1.0 g, 95% or more yield).
[0071] .sup.1H NMR (CDCl.sub.3): .delta. 1.19 (s, 3H,
Ti--CH.sub.3), 1.84 (m, 6H, Cp-CH.sub.3), 1.00.about.2.00 (br, 4H,
diol aliphatic (CH.sub.2), quinoline-CH.sub.2), 2.01 (m, 6H,
Cp-CH.sub.3 and CH.sub.3), 2.61 (m, 2H, quinoline-CH.sub.2), 3.97
(br, 2H, OCH.sub.2), 4.24 (m, 2H, quinoline-NCH.sub.2), 6.71 (m,
1H, aromatic), 6.90 (m, 2H, aromatic) ppm
Comparative Example 1
##STR00008##
[0073] A compound of the above structural formula was prepared
according to the method described in Example 7 of US
20070025158A1.
Preparation of Olefin Copolymer
Experimental Example 1
[0074] Into a 2 L autoclave reactor, a hexane solvent (1.0 L) and
6.4 mmol of 1-octene were added, and then, the temperature of the
reactor was preheated to 120.degree. C. To a 25 mL catalyst storage
tank, the compound of Example 1 (0.5 .mu.mol) treated with
triisobutylaluminum (10 .mu.mol) and a dimethylanilinium
tetrakis(pentafluorophenyl)borate cocatalyst (10 .mu.mol) were
sequentially added and filled (the mole ratio of Al:Ti is 10).
Subsequently, ethylene pressure (35 bar) was added into the
autoclave reactor, and a catalyst composition was injected into the
reactor using high pressure argon gas to progress copolymerization
for 10 minutes. Next, the remaining ethylene gas was taken out and
a polymer solution was added to an excessive amount of ethanol to
induce precipitation. The precipitated polymer was washed with
ethanol and acetone each two or three times, and dried in a
80.degree. C. vacuum oven for 12 hours or more, and then, the
properties were measured.
Experimental Example 2
[0075] Into a 2 L autoclave continuous process reactor, a hexane
solvent (4.53 kg/h) and 1-octene (0.8 kg/h) were filled, and then,
the temperature of the upper part of the reactor was preheated to
150.degree. C. Triisobutylaluminium (0.05 mmol/min), the compound
of Example 1 (0.5 .mu.mol/min), and a dimethylanilinium
tetrakis(pentafluorophenyl)borate cocatalyst (1.5 .mu.mol/min) were
simultaneously introduced into the reactor.
[0076] Subsequently, ethylene (0.84 kg/h) was introduced into the
autoclave reactor, and the same temperature was maintained for 30
minutes or more and then copolymerization was progressed for 8
minutes in a continuous process to obtain copolymer. Next, the
remaining ethylene gas was taken out, and the polymer solution was
dried in a 80.degree. C. vacuum oven for 12 hours or more, and
then, the properties were measured.
Experimental Example 3
[0077] Into a 2 L autoclave continuous process reactor, a hexane
solvent (5.4 kg/h) and 1-butene (0.8 kg/h) were filled, and then,
the temperature of the upper part of the reactor was preheated to
150.degree. C. Triisobutylaluminium (0.05 mmol/min), the compound
of Example 1 (0.5 .mu.mol/min), and a dimethylanilinium
tetrakis(pentafluorophenyl)borate cocatalyst (1.5 .mu.mol/min) were
simultaneously introduced into the reactor.
[0078] Subsequently, ethylene (0.83 kg/h) was introduced into the
autoclave reactor, and the same temperature was maintained for 30
minutes or more and then copolymerization was progressed for 8
hours in a continuous process to obtain copolymer. Next, the
remaining ethylene gas was taken out, and the polymer solution was
dried in a 80.degree. C. vacuum oven for 12 hours or more, and
then, the properties were measured.
Experimental Example 4
[0079] Ethylene-1-octene copolymer was prepared by the same method
as Experimental Example 1, except that 0.5 .mu.mol of the compound
of Example 2 was introduced instead of the compound of Example 1 in
Experimental Example 1.
Experimental Example 5
[0080] Ethylene-1-octene copolymer was prepared by the same method
as Experimental Example 2, except that the compound of Example 2
(0.5 .mu.mol/min) was introduced instead of the compound of Example
1 in Experimental Example 2.
Experimental Example 6
[0081] Ethylene-1-butene copolymer was prepared by the same method
as Experimental Example 3, except that the compound of Example 2
(0.5 .mu.mol/min) was introduced instead of the compound of Example
1 in Experimental Example 3.
Experimental Example 7
[0082] Ethylene-1-octene copolymer was prepared by the same method
as Experimental Example 1, except that 0.5 .mu.mol of the compound
of Example 3 was introduced instead of the compound of Example 1 in
Experimental Example 1.
Experimental Example 8
[0083] Ethylene-1-octene copolymer was prepared by the same method
as Experimental Example 2, except that the compound of Example 3
(0.5 .mu.mol/min) was introduced instead of the compound of Example
1 in Experimental Example 2.
Experimental Example 9
[0084] Ethylene-1-butene copolymer was prepared by the same method
as Experimental Example 3, except that the compound of Example 3
(0.5 .mu.mol/min) was introduced instead of the compound of Example
1 in Experimental Example 3.
Comparative Experimental Example 1
[0085] Ethylene-1-octene copolymer was prepared by the same method
as Experimental Example 1, except that 1.0 .mu.mol of the compound
of Comparative Example 1 was introduced instead of the compound of
Example 1 in Experimental Example 1.
Comparative Experimental Example 2
[0086] Ethylene-1-octene copolymer was prepared by the same method
as Experimental Example 2, except that the compound of Comparative
Example 1 (1.0 .mu.mol/min) was introduced instead of the compound
of Example 1 in Experimental Example 2.
Comparative Experimental Example 3
[0087] Ethylene-1-butene copolymer was prepared by the same method
as Experimental Example 3, except that the compound of Comparative
Example 1 (1.0 .mu.mol/min) was introduced instead of the compound
of Example 1 in Experimental Example 3.
[0088] The catalytic activities and the properties of
ethylene-1-octene copolymer in Experimental Example 1 and
Comparative Experimental Example 1 are shown in the Table 1
below.
TABLE-US-00001 TABLE 1 Comparative Experimental Experimental
Example 1 Example 1 Catalyst compound Comparative Example 1 Example
1 Reaction temperature(unit: .degree. C.) 120 120 Catalyst
compound(unit: .mu.mol) 0.5 1.0 Al(cocatalyst):Ti(catalyst
compound) 10 10 mole ratio 1-octene introduction amount 6.4 6.4
(unit: mmol) Activity 76 75 (unit: kgPOE/mmol Ti hr) Melt index
I.sub.2 1.12 2.56 (unit: g/10 min) Melt index I.sub.10 11.2 29.9
(unit: g/10 min) I.sub.10/I.sub.2 10 11.7 Density 0.862 0.862
(unit: g/ml) Tm 44.1 41.9 (unit: .degree. C.)
[0089] And, the catalytic activities and the properties of
ethylene-1-octene copolymer in Experimental Example 2 and
Comparative Experimental Example 2 are shown in the Table 2
below.
TABLE-US-00002 TABLE 2 Comparative Experimental Experimental
Example 2 Example 2 Catalyst compound Comparative Example 1 Example
1 Reaction temperature(unit: .degree. C.) 150 150 Catalyst
compound(unit: .mu.mol/min) 0.5 1.0 Al(cocatalyst):Ti(catalyst
compound) 50 50 mole ratio 1-octene introduction amount 760 760
(unit: mmol) Yield 1024.2 966.0 (unit: g/h) Activity 48.8 32.2
(unit: kgPE/mmol Ti hr) Melt index I.sub.2 4.21 3.34 (unit: g/10
min) Density 0.869 0.868 (unit: g/ml) Tm 50.7 51.5 (unit: .degree.
C.)
[0090] Referring to Tables 1 and 2, since the dinuclear metallocene
compound of the present invention has a structure wherein single
metallocene compounds are connected by a diether chain, unnecessary
interactions between the metals may be minimized to afford stable
catalytic activity, and thus, it has high activity and can prepare
polyolefin having high molecular weight compared to mononuclear
metallocene catalyst.
* * * * *